Effect of polymer architecture on the efficiency of acyl transfer reactions

A series of spacer-modified polystyrene-supported hydroxamic esters and hydroxamic dithiocarbonic anhydrides were prepared starting from divinyl benzene and ethyleneglycol dimethacrylate crosslinked polystyrene resins through multistage polymer-analogous reactions. Acyl transfer reactions using these polymer-supported hydroxamic acylating agents containing spacer arms of various lengths were carried out. The investigation revealed a sharp increase in reactivity as the length of the spacer arm was increased from zero methylene spacer to five methylene spacers. Investigations were also carried out to correlate the extent of acyl transfer with the nature and degree of crosslinking and the relative polarity of the polymer network. It was found that the extent of functionalization in each of the polymer analogous reactions and the extent of acylation reaction decreased with an increase in the degree of crosslinking. © 1996 John Wiley & Sons, Inc.     

Rh/γ-Al2O3 Catalytic Layer Integrated with Sol–Gel Synthesized Microporous Silica Membrane for Compact Membrane Reactor Applications

An efficient and compact catalytic membrane reactor for reforming of CH₄ was developed by integrating a hydrogen perm-selective silica membrane with an Rh/-Al₂O₃ catalyst layer. The catalytic layer was sandwiched between the outer surface of the -Al₂O₃ support tube and the silica membrane with an aim of improving the heat and mass transfer rates through the system and to simplify the reactor geometry. The system showed improved efficiency for reforming of CH₄ at comparatively lower operating temperatures and steam to C molar ratios than the conventional fixed-bed steam reforming systems. Under optimized conditions, a nearly 25-30% improvement from the equilibrium conversion level was achieved as a result of abstraction of hydrogen from the product stream by the silica membrane integrated with the catalyst layer. The performance of the system was evaluated as a function of various process parameters. Because of the compactness and efficiency, the present system emerges as a promising alternative to the conventional membrane reactors, which possess separate catalytic and membrane units.     

Studies on compatibility of biodegradable starch/polyvinyl alcohol blends

Compatibility of starch/polyvinyl alcohol (PVA) blends, prepared by solution cast method, is dependent on the blend composition. Crystallinity of the blend, as measured by X‐ray diffraction (XRD) and differential scanning calorimeter (DSC), decreases with increase in starch content. Thermogravimetric analysis (TGA) shows that the broadness in the peak width at the degradation region increases with increase in starch content in the starch/PVA blend. Dynamic mechanical thermal analysis (DMTA) reveal that the broadness of the relaxation peaks is due to the partial compatibility of the glycerol plasticized starch/PVA blends. The tensile property decreases with increase in starch content and the 30/70 starch/PVA blend shows maximum ductility in respect to both the percentage of elongation and energy at break. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Thermal and mechanical properties of chitosan reinforced polyhydroxybutyrate composites

The article reports the results of studies on the effect of chitosan (0, 5, 10, 20, 30, and 40 wt %) on thermal and mechanical properties of poly(hydroxybutyrate) composites. The addition of chitosan causes an increase in the glass transition temperature (T_g) while a decrease in the enthalpy of fusion (ΔH_fus), crystallization (ΔH_cry) and percentage of crystallinity as determined by differential scanning calorimeter (DSC). The thermogravimetric analysis reveals that high amount of chitosan decreases the thermal stability of the composites. The Young's modulus of the composite increases and is high for the composite having 40 wt % of chitosan. Increase in the amount of chitosan decreases the elongation at break and impact strength of composites. Finally, the Young's modulus of the composites has been compared with the theoretical predictions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrous RuO(2)-Carbon Nanofiber electrodes with high mass and electrode-specific capacitance for efficient energy storage

We demonstrate a new strategy for the fabrication of supercapacitor electrodes possessing high mass and area-specific capacitance for efficient charge storage, which can be extremely useful for the development of light, compact and high performance supercapacitors for a variety of high power demanding applications. High mass and electrode area specific capacitances were attained by using Hydrous Ruthenium Oxide (HRO)-Carbon Nanofiber (CNF) hybrid electrodes prepared by the deposition of HRO (~31% Ru content) on both the outer and inner surfaces of a cylindrical hollow CNF having open tips. Electrochemical studies of the uniformly deposited HRO nanoparticles on the CNF surface showed a mass specific capacitance of 645 F g(-1) and an electrode specific capacitance of 1.29 F cm(-2) with a HRO-CNF material loading of 2 mg cm(-2) in the supercapacitor electrodes. The mass specific capacitance of pure HRO is 301 F g(-1), whereas the mass specific capacitance of HRO in the HRO-CNF electrode is ~1300 F g(-1), which is very close to the theoretical capacitance of HRO. This enhanced charge storage ability, high rate capability, better cyclic stability and low ESR of the HRO-CNF will be useful for the development of high performance supercapacitors.     

Non-uniform Euler-Bernoulli beams under a single moving oscillator: An approximate analytical solution in time domain

Dynamic responses of simply supported non-uniform beams traversed by a moving oscillator are analysed in this paper. An approximate analytical method based on Rayleigh-Ritz (R-R) formulation is developed. The fundamental approximate mode obtained from R-R method is used in the present formulation to determine the responses of the beam and the oscillator. Effects of surface irregularities on the displacement and acceleration responses of the beam and the vehicle are also analysed. The results are compared with those obtained using Finite element method (FEM). A numerical example is provided to illustrate the validity of the present method which shows that the proposed method is simple, computationally more efficient compared to FEM and gives fairly good results. Though the single-mode approach used in the present paper is a classical one and numerous studies on the responses of uniform beams under moving loads have been reported in the past, its application to non-uniform beams (for which there does not exist any closed form expression for mode shapes) under a moving load, especially a moving oscillator, is presented for the first time.     

Dielectric,Mechanical, and Thermal Properties of Low-Permittivity Polymer–Ceramic Composites for Microelectronic Applications

A new low-permittivity polymer–ceramic composite for packaging applications has been developed. The ceramic-reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Low-loss, low-permittivity Li₂MgSiO₄ (LMS) ceramics prepared by the solid-state ceramic route were used as the filler to improve the dielectric properties of the composites. The relative permittivity and dielectric loss were increased with the increase in the ceramic loading at radio and microwave frequencies. The mechanical properties and thermal conductivity of the Li₂MgSiO₄-reinforced polymer–ceramic composite were also investigated. The stability of the relative permittivity of polymer–ceramic composites with temperature and frequency was investigated. The experimentally observed relative permittivity, thermal expansion, and thermal conductivity were compared with theoretical models.     

Thermal and rheological behavior of acrylonitrile–carboxylic acid copolymers and their metal salt complexes

The influence of acrylic, methacrylic, and itaconic acid comonomers in the nitrile oligomerization of acrylonitrile copolymers has been studied by DSC and DSC‐FTIR in air and nitrogen atmospheres. Addition of metal salts in poly(acrylonitrile–acrylic acid) copolymer, PA on thermal and rheological behavior has also been reported. Incorporation of CuSO₄, FeSO₄, ZnSO₄, and Al₂ (SO₄)₃ (1 to 5 wt %) salt in the polymer solution affects its solubility in DMF. The complexes of PA with zinc sulphate, took a longer time to dissolve in DMF, whereas the complexes with Fe(SO₄) and Al₂(SO₄)₃ are almost insoluble in DMF, perhaps due to intermolecular crosslinking. Addition of these metal salts to the PA solution also affects its Brookfield viscosity. The viscosity of 10 wt % polymer solution increases from 400 centipoise (Cps) to 1090 Cps for complex with 5% FeSO₄ (on the weight of dope solids) and 690 Cps for Al₂ (SO₄)₃ and 906 cps for ZnSO₄ complex. However, for CuSO₄ salt complex this value is 770 Cps. FTIR spectra shows the participation of COOH and CN group in the complex formation, which is responsible for enhanced Brookfield viscosity. Thermal behavior of the polymer–metal salt complex showed that these salts also affect the exothermic reaction. The initiation of cyclization reaction takes place at a lower temperature compared to neat acrylonitrile–acrylic acid copolymer. However, the heat liberated per unit time in N₂ atmosphere in case of neat polymer is 6.3 Jg⁻¹ min⁻¹, which reduces to 5.5 Jg⁻¹ min⁻¹ in the case of the PA/Al complex, confirming the role of Al₂ (SO₄)₃ in retarding the rate of cyclization reaction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 567–582, 1999     

Pt-MoOx-carbon nanotube redox couple based electrocatalyst as a potential partner with polybenzimidazole membrane for high temperature Polymer Electrolyte Membrane Fuel Cell applications

A redox couple based electrocatalyst comprising of Pt-Multi Wall Carbon NanoTube (Pt-MWCNT) promoted with molybdenum oxide (MoO_x, 2 < x < 3) nanoparticles was prepared. The objective was to effectively organize the Pt-MoO_x interface on the smooth MWCNT surface to overcome the practical difficulties associated with establishing such interface with Pt dispersed on carbon morphologies possessing surface irregularities. The present study revealed the importance of stringent controlling of the additive level for maintaining a balanced bifunctional behavior of the catalyst combination through the synergistic effects by the components and the need of a proton conducting membrane operable at high temperature to get better output from the Polymer Electrolyte Membrane Fuel Cell (PEMFC) systems. An indigenously developed polybenzimidazole (PBI) membrane was used to fabricate a membrane electrode assembly (MEA) as it can be operated at higher temperatures compared to that of Nafion membranes. MoO_x additive level was carefully controlled by monitoring the active Pt area by cyclic voltammetry. All prepared electrocatalysts were characterized by using HRTEM, XRD and XPS to get information on dispersion and morphology, crystalinity and oxidation state of different elements, respectively. The system prepared with 5% MoO_x addition with respect to Pt (hereafter Pt-MoO_x(5%)-MWCNT) displayed balanced active Pt area and excellent oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities. Rotating Disk Electrode (RDE) system was extensively utilized to understand the ORR kinetics and the favorable role of MoO_x as the promoter in the reaction. The kinetic current (j_k) measured at 0.02 V vs. Hg/Hg₂SO₄ electrode from the Koutecky-Levich plots was 9 times higher and the apparent activation energy during single cell evaluation was 27 kJ/mol lower for the MoO_x promoted system, compared to the system without the additive. A higher operating temperature significantly favored the cell performance by a combined effect of enhancement in proton conductivity of the PBI membrane and possible kinetic benefit by the well postulated oxygen spill over effect by the MoO_x type systems in some combinations involving such systems.     

Hydrogen-Induced Cracking (HIC) of Hardened and Tempered Steel Fastener Used in Space Application

Cadmium-plated 0.35C–3.5Ni–1.5Cr–0.5Mo steel threaded fasteners of 1230 MPa properties class are used for aerospace applications. These fasteners were torqued to 13 N·m. Few fasteners parted into two pieces while in use under sustained assembly load for a period of 50 days. The fracture surface of the failed fasteners had two distinct regions when viewed under microscope at higher magnification. Fractography revealed that the larger region consisted of predominantly intergranular features, whereas the smaller region had features of microvoid coalescence. From the metallography evidences it was concluded that the fastener failure was due to hydrogen embrittlement. Electro-deposit of cadmium was identified to be the main source for hydrogen entrapment, which could not be compelled completely by post-plating baking treatment.